Characterization of quasi-reversible surface processes by square-wave voltammetry

Abstract

Quasi-reversible redox reactions of species bound to the electrode surface are characterized by standard potential, transfer coefficient, and rate constant. Numerical calculations show that these nonlinear parameters affect the square-wave voltammetric response in complex ways yielding a variety of peak shapes. For typical analytical conditions [step height (nΔE s )=10 mV, amplitude (nE sw )=50 mV], voltammograms fall into three types depending upon the dimensionless rate constant κ o =K o t p , where κ o is the first-order rate constant (s -1 ) and t p (s) is the pulse width of the waveform